Process for the manufacture of new condensates

ABSTRACT

This invention provides new condensation products which are obtained by reacting a monocyclic or dicyclic heterocyclic compound having 5 to 7 ring members, at least two members being nitrogen and at least two halogen atoms being linked directly with the carbon atoms of the heteroring, with a thiourea compound or an alkali or ammonium hydrogensulfide and a mono- or dialkanolamine. These condensation products are useful as agents for textile finishing, especially for improving crease resistance and abrasion resistance.

United States Patent Buhler et a1.

[4 1 Aug. 12, 1975 PROCESS FOR THE MANUFACTURE OF NEW CONDENSATES Inventors: Arthur Buhler, Rheinfelden; Hans Ulrich Schutz, Basel; Dieter Mausezahl, Biel-Benken; Melvin Harris, Dornach; Christian Guth, Basel, all of Switzerland Assignee: Ciba Geigy AG, Basel, Switzerland Filed: Aug. 15, 1973 Appl. No.: 388,517

Related US. Application Data Division of Ser. No, 104,142, Jan. 5, 1971, Pat. No. 3,776,767, which is a continuation of Ser. No. 768,495, Oct. 1 7, 1968, abandoned.

Foreign Application Priority Data Oct. 24, 1967 Switzerland 14826/67 US. Cl. 260/67.5; 117/1394; 117/1395 A; 117/161 LN; 260/29.4 R; 260/29.4 VA; 260/676 R; 260/67.6 C; 260/69 F; 260/70 R; 260/70 M; 260/249.6; 260/249.8

Int. Cl C08g 9/32 Field of Search 260/67.5, 67.6 R, 67.6 C, 260/69 R, 69 F, 69 N, 70 R; 117/1394,

[56] References Cited UNITED STATES PATENTS 3,079,279 2/1963 Van Loo 1 17/139.4 3,789,040 1/1974 McKeown et a1. 260/69 R X FOREIGN PATENTS OR APPLICATIONS 967,251 10/1950 France 1,242,188 8/1960 France 562,593 11/1957 Belgium Primary Examinerl-loward E. Schain Assistant ExaminerW. C. Danison Attorney, Agent, or Firm.loseph G. Kolodny; Edward McC. Roberts; Prabodh l. Almaula [57] ABSTRACT These condensation products are useful as agents for textile finishing, especially for improving crease resistance and abrasion resistance.

4 Claims, No Drawings PROCESS FOR THE MANUFACTURE OF NEW CONDENSATES This application is a division of application Serial Number 104 142, filed Jan. 5, 1971, now US. Pat. No. 3,776,767, which in turn is a continuation of application Ser. No. 768,495, filed Oct. 17, 1968, and now abandoned.

It has been found that valuable new condensates are obtained that are capable of substantially counteracting the impairment of the mechanical properties occurring when finishing cellulosic textile materials with aminoplasts, when in an aqueous medium at a temperature from l to +30C, in each case at a molecular ratio of l 2 to l 0.5, preferably from l 1.5 to l 0.5, a colourless heterocyclic compound that contains at least 2 nitrogen atoms in the hetero ring and at least 2 halogen atoms linked with carbon atoms of the hetero ring, is reacted with A. a thiourea compound that contains at least one hydrogen atom linked with nitrogen, preferably thiourea itself, or with an alkali metal or ammonium hydrogensulphide and B. a monoor di-alkanolamine containing 1 to 4 earbon atoms, preferably with monoor diethanolamine, the reaction is then finalized at a temperature from 30 to 100C, preferably from 45 to 70C and, if desired, water is distilled out of the mixture formed.

The heterocyclic compound used as starting material in the present process must be practically colourless and contain at least one, preferably only one, heterocycle which may be altogether the only ring of the compound or, for example, may also contain a fused-on aromatic six-membered ring. Specially useful are compound with six-membered heterorings, especiallly those whose ring contains 2 or 3 nitrogen atoms and 4 0r 3 carbon atoms, such as pyridazine, pyrimidine, quinazoline and especially l,3,5-triazine compounds. These compounds contain at least 2 halogen atoms linked with carbon atoms of the hetero ring, for example bromine or preferably chlorine atoms. As relevant examples there may be mentioned trichlorpyrimidine, tetrachloropyrimidine, 2,4-dichloroquinazoline, 2,4,6-tribromol ,3,5-triazine and in the first place 2,4,- 6-trichlorol ,3,5'triazine (cyanuric chloride).

As further starting materials there are required a thiourea compound containing at least one hydrogen atom linked with nitrogen, or preferably thiourea itself or an alkali metal or ammonium hydrogensulphide, as well as a monoalkanolamine or dialkanolamine containing l to 4 carbon atoms, preferably monoor diethanolamine.

The reaction is performed in an aqueous medium that may contain apart from water organic solvents, especially those which are water-miscible. There may be mentioned lower alcohols and acetonev No specific sequence of the reaction stages is prescribed, that is to say, the heterocyclic compound may be reacted first with the sulphur-containing compound or first with the alkanolamine.

For the reaction of every mol of component (A) or (B) with the heterocyclic compound 1 mol of alkali or a slight excess in form of an aqueous alkali metal hydroxide or carbonate solution is added to the reaction mixture, either in one lot or portionwise.

The reactions are performed within the temperature range from l0 to +30C; in the presence of an organic solvent the reaction temperature may be below 0C, whereas when purely aqueous reaction media are used it is advantageous to react at 0C or slightly higher.

It is advantageous to start with the second reaction step in each case only after the first reaction is substantially complete; this is approximately the case when after addition of the alkali, or of its last portion, the reaction medium reveals a pH value of about 7. The reaction is then finalized at a temperature from 30 to 100C, preferably from 40 to C, and may be terminated after 2 to 3 hours. The pH value of the reaction mixture during this time should be within the neutral or slightly alkaline region. A drop in pH value impairs the solubility of the reaction product substantially and can be prevented by adding more alkali. The condensates are also obtained, when in an aqueous medium at a temperature from 10 to +25C at a pH value from 6 to 9 and at a molecular ratio from 1 1.5 to 1 0.5, a colourless heterocyclic compound that contains at least 2 nitrogen atoms in the hetero ring and at least 2 halogen atoms linked with carbon atoms of the hetero ring, is reacted with a thiourea compound and on completion of this first reaction stage, without intermediate separation, for every mol of heterocyclic halogen compound used 0.5 to 1.5 mols of a monoalkanolamine are added, while maintaining a pH value from 6 to 10 and keeping the temperature of the reaction medium first for at least 8 hours at 30 to 50C and then for at least 5 hours at 60 to 65C and, if desired, the water is distilled out of the mixture formed.

When the starting material used is cyanurie chloride, then, in general, for 1 mol each of this halogen compound a total of about 4 mols of monoacidic base, thus for instance 3 mols of alkali metal hydroxide and lmol of alkanolamine, is consumed. The amount of Water used as reaction medium may be freely chosen within a wide range, advantageously so that, on one hand, the reaction mixture is easy to stir from the start and the risk of heating beyond the prescribed temperature range is obviated and that, on the other hand, excessive dilution does not make the practical performance problematic. Since as a rule the heterocyclic halogen compounds are sparingly soluble in the water serving as reaction medium, it is advantageous first to convert them into a finely distributed state, which can be done in known manner by dissolution in an organic watermiscible solvent such as acetone and pouring the solution out over ice. As mentioned above, the molecular ratio heterocyclic halogen compound sulphurcontaining compound should range from 1 2 to l 0.5, preferably from 1 1.5 to l 0.5, and the molecular ratio of heterocyclic halogen compound alkanolamine should likewise be within the range from 1 z 2 to l 0.5, preferably from l 1.5 to l 0.5. Especially with cyanuric chloride particularly good results are ob tained by using equimolecular proportions or amounts of the three reactants differing only little therefrom.

On completeion of the reaction the resulting product can be used as it is for the purpose indicated above. ln view of the concentration of the mixture, which is not very high at the end of the reaction, it is, however, advisable to remove the water completely or partially by distillation under vacuum. In this manner generally stable products are obtained which are at most only slightly tinted and are readily and completely soluble in water.

The products obtained by the process described above are suitable, as has already been said, for use in combination with aminoplasts in textile finishing, especially for improving the shape retention. Particularly suitable for such a treatment is textile material of cellulose, if desired in combination with other fibres, for example polyester fibres. Therefore, according to a preferred use of the products of this invention textile materials are impregnated with an aqueous preparation containing a curable aminoplast precondensate, a curing catalyst and a condensate of the composition defined above, whereupon the textile material is dried and hardened by treatment at an elevated temperature.

Aminoplast precondensates are adduts of formaldehyde with methylolable nitrogen compounds. In this connection there may be mentioned amino-1,3,5- triazines such as N-substituted melamines, for example ammeline. guanamines, for example benzoguanamine or acetoguanamine. Further suitable are symmetric alkyltriazines, biuret, thiourea, alkylcarbamates, guani dine, alkylor aryl-ureas and -thioureas, alkylene areas or diureas, for example ethylene urea, propylene urea or acetylene diurea; 4,5-dihydroxy-imidazolidone-2 and its derivatives, for example the 4,5-dihydroxyimidazolidone-Z substituted in 4-position on the hydroxyl group by the residue -CH CH CON- HCH -OH. The methylol compounds of urea and of melamine are preferred and in the case of melamine compounds those ofa low or high degree of methylolation may be used. It is also possible to use compounds whose methylol groups are more or less completely etherified, for example, with methyl groups.

As curing catalysts the conventional acid or potentially acid compounds may be used, such a ammonium chloride, magnesium chloride or zinc fluoroborate.

Particularly valuable results are also obtained when the preparation used for finishing the textile materials contains in addition to the aminoplast precondensate, the curing agent and the condensate of this invention also an emulsion polymer prepared from an N- methylolamide of an afi-ethylenically unsaturated carboxylic acid or an ether of such a methylolamide and an alkaline earth metal salt of an afi-ethylenically unsaturated monocarboxylic acid, especially the copolymers, obtained in an aqueous emulsion, from a. 0.25 to by weight of an alkaline earth metal salt of an a,B-ethylenically unsaturated monocarboxylic acid (for example calcium acrylate),

0.25 to 30 percent by weight of an N- methylolamide or N-methylolamide ether of an a,B-unsaturated monoor dicarboxylic acid (for example acrylic acid methyldamide, methacrylic acid methylolamide or the methyl ethers of these methylolamides).

c. 99.5 to 60 percent by weight of at least one further copolymerizable compound, for example an ester of acrylic or methacrylic acid and an alkanol such as methanol, ethanol, n'butanol, acrylic acid tertiary butylamide, vinylidenechloride, vinylacetate, acrylonitrile, styrene.

Depending on the purpose to be served by the finish the aqueous preparations may contain further ingredients, for example hydrophobizing agents, suitable optical brighteners, wetting agents, dispersants or flameproofing agents, especially phosphorus compounds such as dialkylphosphono-propionic acid methylolamides. In very many cases it is also advisable to add, for example, a nonionic agent that produces a soft handle, for example an aqueous emulsion of a methylolmelamine alkyl ether modified by stearic acid alkylolamide residues.

The proportions of the ingredients of the aqeous preparations may vary within wide limits and may be adapted to the purpose in hand. In general it is indicated to use for 10 parts of aminoplast precondensate l to 4 parts of condensate from heterocyclic halogen compound, thiourea and alkanolamine. Otherwise, the textile material may be treated in the usual manner. For example, undyed or dyed fabric or tricot may be impregnated on a padder with the preparation and, advantageously after an intermediate drying operation at a temperature of up to C, subjected to a treatment with dry heat of C for 2 to 20 minutes, the temperature and the duration of the treatment being adapted to the purpose of the treatment which may be, for example, an improvement of the wet fastness properties for direct dyeing dyestuffs, an anti-crease finish or permanent shaping (permanent press). The finishing operation may also be combined with a dyeing operation, for example so that the impregnating solution further contains a dyestuff which, by virtue of special substituents, is reactive towards the fibre or more especially towards the aminoplast precondensate and, by

virtue of this property, is fixed on the substrate during the heat treatment or even before it.

As is known an aminoplast resin finish impairs the mechanical properties of cellulosic fibrous materials, especially their tensile strength and abrasion resistance; in general the loss in strength is the greater the higher the content of aminoplast and the more energetic the hardening is. As mentioned above, these serious drawbacks can be substantially prevented with the aid of the new condensates or at least they can be reduced to an acceptable degree. In addition it has been observed that these condensates improve the soil release from the fibre.

Example 1 A solution of g (1 mol) of cyanuric chloride in 1 litre of acetone is poured over a mixture of l litre of water and 1 kg of ice and the precipitated cyanuric chloride is filtered off. The paste is introduced into a solution which has been prepared at 45C from 76 g 1 mol) of thiourea and l /2 litre of water and has then been cooled by adding 1/2 kg of ice. By dropping in a 5N-sodium hydroxide solution the pH value is maintained at 6.7 to 6.9 during this first condensation stage and the temperature is maintained at 8 to 10C by indirect cooling. After about 5 hours and a consumption of about 3.5 mols of sodium hydroxide the pH value remains constant, and practically everything is dissolved in the reaction mixture. Then one lot of 61 g (1 mol) of monoethanolamine is added and the solution, which is now clear, is heated in a second condensation stage for 15 hours at 35 to 40C and in a third stage for 8 hours at 55 to 60C. During this time further sodium hydroxide solution is added as and when required so that the pH value remains constant at 7.0, for which about 0.5 mol of sodium hydroxide is needed. Finally, the solution is evaporated to dryness at 90 to l0OC under vacuum and the residue is ground in a ball mill,

5 to furnish 410 g of a faintly yellowish, readily watersoluble hygroscopic powder condensate Al i Apart from product A the following Table l i'sts further condensates obtained in this manner, together 100 ml of acetone and at C 6.1 g (0.1 mol) of mono-. ethanolamine are added in one lot. By dropping in 5.3 g (0.05 mol) of anhydrous sodium carbonate in 15 ml of water during 1 hour the pH value of the reaction with the appropriate data for their manufacture: mixture is maintained at about 7.

Table l Quantity in nir-ls 1st stage 2nd stage 3rd stage Working up (yanuric thiourea ethanoltemp. hrs. pH-valuc temp. hrs. pH- temp. hrs. pH- 15 evaporate chloride amine \"aluc value in vacuo at A l l 1 8-10 5 6.7-6.) 35-40 15 7 55-60 8 7 E 90-100 B l 1 1 0-10 X 6.0-6.5 35-40 1-1 7 55-60 9 7 E 90-100 C l l 1 0-12 2 8-) 35-40 15 7 55-60 8 7 E 90-100 D l l 1 0-10 4%; 7 35-40 15 7 55-60 8 7 E 90-100 l: l l 1 11-8 5 7 35-40 14 7 55-60 7 [i )0- 100 F l 1.5 0.5 0-10 8 7 35-40 13 7 55-60 7 7 E 90-100 (i 05 1.5 0-10 22 7 35-40 I: 7 55-60 N 7 F. 90-100 H 2 I Z 0-12 14 7 35-40 18 7 55-60 8 7 E 90-100" "filtering off insoluble residue before Example 2 Then 7.6 g (0.1 mol) of thiourea and 20 ml (0.1 mol) A solution of 18.5 g (0.1 mol) of cyanuric chloride in 100 cc of acetone is poured out over a mixture of 0.1 litre of water and 0. 1 kg of ice, and the precipitated cyanuric chloride filtered off. The paste is introduced into a solution which has been prepared at 45C from 7.6 g (0.1 mol) of thiourea and 50 m1 of water and then cooled by adding 50 g of ice thereto. In this first condensation stage the pH value is maintained at 6.7 to 6.9 by dropping in a 5N-sodium hydroxide solution and the temperature is kept at 8 to C by indirect cooling. After about 5 hours and a consumption of about 3.5 mols of sodium hydroxide the pH value remains constant and practically all has dissolved in the reaction mixture. One lot of 10.5 g (0.1 mol) of diethanolamine is then added and the reaction mixture heated to 55 to 60C while adding another 10 ml of 5N-sodium hydroxide solution (0.05 mol) and then heated at this temperature with stirring for 5 hours.

The solution is then evaporated to dryness at 60C under vacuum, to yield 46 g ofa pale yellowish, readily water-soluble powder: condensate J Example 3 A suspension of 18.5 g (0.1 mol) of cyanuric chloride in 100 ml of alcohol is cooled to 5 to 10C. One lot of 6.1 g (0.1 mol) of monoethanolamine is added; during minutes ml of 5N-sodium hydroxide solution (0. 1 mol) are dropped in and the reaction mixture is stirred for about 1 hour at the same temperature until a constant pH value of about 2.7 has been established.

On addition of 7.6 g (0.1 mol) of thiourea and 30 ml of SN-sodium hydroxide solution (0.15 mol), in each case in one lot, the pH value of the reaction mixture temporarily reaches 1 l which drops again to 7 after another 30 minutes reaction, during which the temperature is raised to 30 to 40C. Then another 20 ml of 5N- sodium hydroxide solution are added and the reaction terminated after stirring for 2% hours.

The resulting colourless suspension is evaporated to dryness at 40C under vacuum,'to leave 40 g of a pale yellow, readily water-soluble product: condensate K.

Example 4 18.5 Grams (0.1 mol) of cyanuric chloride are suspended in 200 ml-of a mixture of 100 ml of water and of SN-sodium hydroxide solution are added. When the pH value has dropped to 7, the temperature is raised to 50C and the reaction finalized by stirring for minutes, during which another 40 ml (0.2 mol) of 5N- sodium hydroxide solution are gradually added. The resulting reaction mixture is evaporated to dryness under vacuum, to yield 40 g of a readily water-soluble condensate: condensate L.

Example 5 Another 20 ml (0.1:mol) of 5N-sodium hydroxide are added and the reaction continued for 3 hours at the same temperature, whereupon it is terminated, and the pH value adjusts itself at 10. The reaction mixture'is first filtered to remove. the insoluble components(5.5 g of a yellowish substance) and the filtrate is then evaporated to dryness at 60C under vacuum, to yield 26.5 g of a white powder: condensate M.

Example 6 Aqueous padding liquors are prepared with the use of the substances listed below:

a. Aminoplast precondensate 50 percent aqueous solution of a mixture of dimethylolethylene urea and methyl ether of a highly methylolated melamine.

b. Softening agent 30 percent dispersion of a methyl ether (modified .with stearic acid alkanolamides) of a highly methylolated melamine.

c. Copolymer 27 percent aqueous emulsion ofa copolymer from 80 parts of acrylic acid n-butyl ester, 1 3 parts of vinylidenechloride, 6 parts of acrylic acid methylolamide and 1 part of calcium acrylate.

d. Condensate prepared as described in Example l from cyanuric chloride, thiourea and monoethanolaminc: condensate A.

Mercerised and bleached cotton popelin is then impregnated with padding liquors, whose composition is shown in Table ll, to a weight increase of 60 percent, referred to the original weight of the fabric. The fabric is dried at:60 to 80C and then heat-treated for 4% minutes at 155C, then washed for 5 minutes in a boil ing sodium carbonate solution of 0.2 percent strength, rinsed in cold water and dried.

and heated for 13V minutes at 170C. The fabric is then washed for S minutes in a boiling percent sodium carbonate solution. rinsed in cold and dried.

Example A Aqueous padding liquors are prepared with the use of the under-mentioned substances:

a. Aminoplast precondensate 50 percent aqueous solution of a mixture of dime thylol-ethylene urea and methyl ether of a highly methylolated melamine. b. Softening agent percent aqueous dispersion of a methyl ether (modified with stearic acid alkanolamides) of a highly methylolated melamine.

Table II (a) Aminoplast I I50 150 150 100 100 100 l()() precondensatc g/litre (b) Softening agent g/lltrc 3t) 3t) 3U 30 3t) 3t) 3t) 30 (e) Copolymer emulsion g/litre 4t) 4t) 4t) 40 (d) Condensate A g/litre 4t) 4t) -U) 4t) MgCI hH O g/litre l) l) l) l) [3 l3 l3 l3 CH COOH. 4() g/litre ()5 ()5 ()5 0.5 0.5 ()5 ()5 ()5 pH of padding liquor 5.6 (3.1 5,6 (v.2 5.6 (x3 5.6 (1.2 tensstrcngth (/5 l l l()() 43 (7i 5t) (il (I5 54 abrasion res.t/ Z) ltlt) l8 ()5 2H 73 43 8*) 54 I05 Cl'LilSL' RL .1. itt3) 5() I31) I13 137 I24 ll) ltll) 114 ill) crease angle. wet in"4) 59 lltl 111 I37 IZH ll) ll l24 l25 l Measuring the tensile strength ol'specimens 25 cm St) cm b increasing loads until the l'abrle tears (SNY 934M 'l be loud re uired to bring this about is taken The figures in columns I to N indicate ho tnan 'i of this load are needed to cause the treated fa ric samples to tear.

as llllli for the untreated fabric.

2) For m "\suring the abrasion re. re\'ol\e' at a constant s ed. The number ot'ubrashe rotations tn) are c untreated material (m). From the results obtained the abrasion resistance values (A) or the treated fabric specimens are calculated; A L It) es oltabric. cut diagonall across the fibres. measuring Io mm 44 mm are folded parallel Al'ter 5 minutcs loading and 1 hours reeo\ cf} the test specimens are introduced into an 3 1,4 i To determine the crease angle dr and c\'enl moistened rectangular piec to the short side. placed in between glass plates and loaded \tith Z kg-weights.

angle measuring instrument ot'comentionul design and the crease angle is measured Example 7 nee a loaded ubrasbc element (brushes ith ")lull bristles) performs a constant re\olution on the test specimen hieh likewise ounted that are needed to hole the tested material. alter htning ascertained this number \\ith c. Copolymer 27 percent aqueous emulsion ofa copolymer from parts of acrylic acid nbutyl ester, 13 parts of vinylidenechloride, 6 parts of acrylic acid methylolamide and 1 part of calcium acrylate. d. Wetting agent 25 percent aqueous solution of an adduct of pnonylphenol with 9 mols of ethylene oxide. e. Brightening agent of the formula Table [II t) I Z 3 4 (a) Aminoplast precondcnsate g/litre Ht) 1-H) l-lt) l-tt) (b) softening agent g/litre 30 3t) 3t) 3t) (c) copol \'mer g/litrc 4t) 4!) (d) condensate A g/litre 40 4t) Zn(N();,) .6H O g/litre l3 l3 l3 l3 pH-value of padding liquor 4.5 5.] 4,0 s 1 tensile strength '1; l I5 5] 2s S1 abra. on resistance 2) (1 4t) 5 42s crease angle. dr \'.in 3) 143 I20 14) 132 crease angltxwet. in 4) I24 I l2 l3] 1 l9 Concerning l). I I. 31 and J The tueasuring'id"t' ies'e \alue has been explained lollouing upon 'l .ible ll.

f. One of the following condensates:

l. Condensate from cyanuric chloride, thiourea and monoethanolamine. prepared according to Example l: condensate A.

2. Condensate from cyanuric chloride, monoethanolamine and thiourea, prepared according to Example 3: condensate K.

3. Condensate from cyanuric chloride, sodium hydrogen-sulphide and monoethanolamine, prepared according to Example condensate M.

g. Magnesium chloride hexahydrate (MgClbH o).

ing 0.2 percent sodium carbonate solution, rinsed in cold water and dried.

We claim:

1. Textile finishing compositions for improving the crease and abrasion resistance of textile materials containing (1) a curable aminoplast precondensate, (2) a condensation product obtained by reacting A. cyanuric chloride with B. a member selected from the group consisting of thiourea, sodium-, potassiumand ammonium hydrogensulfide, and

Mercerized and bleached cotton popelin is imprega member Selected from the group Conslstmg of a nated liquors composed as Shown in Tamonoalkanolamtne and a dialkanolamine Wlth l O bles IV, V and VI to a weight increase of 60% referred 4 Carbon atoms In an aqeous medium at a p l O O to the original weight of the fabric. After having been mm from dbout 10 to 30 C at 4 molecular dried at 60 to 80C the fabric is heat-treated for 4 /2 for (B) as as for (C) from 1:2 to 1:05, minutes at 155C, then washed for 5 minutes in a boilfinallzmg the reaction at temperatures from to Table IV (a) Aminoplast prccondensatc g/litre I50 150 I50 150 (h) Softening agent g/litre 3t) 3t) 30 30 (e) (opolymer emulsion g/litre 4t) (d) Wetting agent g/litre 3 3 3 3 (e) Bri htening agent g/litre 3 3 3 3 (f) Condensate A g/litre It) ltl (g) Mg('l. ..oH. g/litre l5 l5 l5 l5 pH-value of the padding liquor 53) 5.9 5.9 5.) tensile strength ('4 l lllt) m (w 63 (1) abrasion resistance (.4 I) l()() l) 5) 39 I03 crease angle in (a) dry 3) 53 I33 122 130 127 (h)\\'et 4) (15 ll 12] I24 126 l l to -11. l'hese \alues are measured as deselihed l'ollouing 'lahle II.

Table V l 2 3 4 (a) Aminoplast preeondensate g/litre I I50 I50 I50 (b) Softening agent g/litre 3t) 3t) 3t) 30 (e) ('opol \mer emulsion g/litre 4() 40 (d) Wetting agent g/litre 3 3 3 3 (e! Brightening agent g/litre 3 3 3 3 ll! (ondensate K g/litre 5 5 (g) Mg("l. ..oH. g/litre l5 l5 l5 l5 pH-\'alue ol' the padding liquor 5.) 5.) 5.) 5.) tensile strength J I J ltlt) (13 (w (13 72 abrasion resistance (J I) lllll l) 39 SN crease angle in (a) th 3) 53 I33 I23 I30 (hlwet 4) (i5 llo ill) I24 ll7 Tahle Vl (a) Aminoplast Pl'CL't lltlCllh'ltlL g/I I50 150 lit) (Ii) Softening agent g/l 3t) 3t) 3t) 30 (c) ('opol mer emulsion g/l 4U 40 (d) Wetting agent g/l 3 3 3 3 tel Brightening agent g/l 3 3 3 3 ll) Condensate M g/l It) It) lg) .\lg('l. oH. g/l l5 l5 l5 I5 pH-Yalue ol' the padding liquor 5.) 5.) 5.) tensile strength I; l I ll 63 h) (\3 7] abrasion re nice ('1' l I) l 1) 4R 3) )4 crease angle in la1dr 3| 53 I33 ll) I30 I27 (h) \\'et 4; \5 llli ll) I14 I20 I l to 47 l'hese \alnes are mea ured as deserihed folliming upon lahle ll 1 1 100 C and removing water from the resulting mixture by distillation, and (3) a curing catalyst, the ratio by weight of aminoplast precondensate: condensation product being from about l:l to :4.

2. Compositions according to claim I, wherein the aminoplast precondensate comprises an adduct of formaldehyde with a nitrogen compound reactable therewith to form an N-methylol group.

3. Compositions according to claim 1, wherein the curing catalyst is a member selected from the group consisting of magnesimn chloride, ammonium chloride, zinc nitrate and zinc fluoborate.

4. Condensation product according to claim 1, ob tained by reacting ture by distillation. 

1. TEXILE FINISHING COMPOSITION FOR IMPROVING THE CREASE AND ABRASION RESISTANCE OF TEXTILE MATERIALS CONTAINING (1) A CURABLE AMINOPLAST PRECONDENSATION (2) A CONDENSATION PRODUCT OBTAINED BY REACTING A CYANURIC CHLORIDE WITH B. A MEMBER SELECTED FROM THE GROUP CONSISTING OF THIOUREA, SODIUM-, POTASSIUM- AND AMMONIUM HYDROGENSULFIDE, AND C. A MEMBER SELECTED FROM THE GROUP CONSISTING OF A MONOALKANOLAMINE AND A DIALKANOLAMINE WITH 1 TO 4 CARBON ATOMS IN AN AQEOUS MEDIUM AT A TEMPERATURE FROM ABOUT 10* TO 30*C AT A MOLECULAR RATIO FOR (B) AS WELL AS FOR (C) FROM 1:2 TO 1:0.5, THE FINALIZING THE REACTION AT TEMPERATURES FROM 30* TO 100*C AND REMOVING WATER FROM THE RESULTING MIXTURE BY DISTILLATTION, AND (3) A CURING CATALYST, THE RATIO BY WEIGHT OF AMINOPLAST PRECONDENSATE: CONDENSATION PRODUCT BEING FROM ABOUT 10:1 TO 10:4.
 2. Compositions according to claim 1, wherein the aminoplast precondensate comprises an adduct of formaldehyde with a nitrogen compound reactable therewith to form an N-methylol group.
 3. Compositions according to claim 1, wherein the curing catalyst is a member selected from the group consisting of magnesium chloride, ammonium chloride, zinc nitrate and zinc fluoborate.
 4. Condensation product according to claim 1, obtained by reacting A. cyanuric chloride with B. a member selected from the group consisting of thiourea, sodium-, potassium- and ammonium hydrogensulfide, and C. a member selected from the group consisting of a monoalkanolamine and a dialkanolamine with 1 to 4 carbon atoms in an aqeous medium at a temperature from about -10* to +30*C at a molecular ratio for (B) as well as for (C) from 1:2 to 1: 0,5, then finalizing the reaction at temperatures from 30* to 100* C and removing water from the resulting mixture by distillation. 